LU86991A1 - NONAQUEOUS LIQUID COMPOSITION OF NON-IONIC LAUNDRY DETERGENT CONTAINING A PERSONAL BLEACHING AGENT AND A LIQUID ORGANIC BLEACHING ACTIVATOR AND METHOD FOR THE USE THEREOF - Google Patents

Description

52.689 --- £ Λ 'j | GRAND DUCHY OF LUXEMBOURG.

Patent No ^ ^ T. ^ *. Minister of September 9. 1987 of Economy and the Middle Classes

Title, issued Intellectual Property Service

Z 6 ................................ 0¾¾ LUXEMBOURG

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Invention Patent Application <& · "-" · ----------------------------------- (1 ) * I. Request

The ..... so-called society; COLGATE-PALMOLIVE COMPANY, 300 Park Avenue / (2) NEW YORKf NY 10022 ........ (United States of America), represented by „Monsieur Jacques de Muvser, acting as agent ---- -------------------- 1 -----: - (3) deposit) this new one. septeipbre-U9-0.0 _ eighty-seven __ (4) at ... .15 ________ hours, at the Ministry of the Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent for invention : —SjCQn ^ QR.1 ±( Qn_J_iqiiid.fi.iiion ... aqueous non-ionic detergent (5) ...... for washing powder containing a bleaching agent of the persel type ....... and. .a ...... activator of bleaching ..... organic liquid and process for its use. "___________________________________________________________________ 2. the description in French __________ language _________________________ of the invention in triplicate; 3 .......... ........................................ drawing boards, in triplicate; 4. the receipt of the fees paid to the Luxembourg Registration Office on September 9, 1987; 5. the delegation of power, dated .N.ew .-. X.ork __________________________ on July 28, 1987 6. the successor document ( authorization); declare (s) assuming responsibility sability of this declaration, that the inventor (s) is (are): (6) ........ 1 ________ Guy ..... BR0ZE..f ._ .. 3.2 .... ... rue _ „C 1 a skin, ....... B-433.0 ....... GRACE-HQLLQGNE, Belgium ........ 2 ...... Daniell. e ~ BASirXN .., 1 i ... rue ..... de .. „1 a ..... Hayo..ul.le. /. Br4632 SOUMAGNE, ....... —Belgium -------------------------------------- -----------------------------; ______________ claims (s) for the above patent application the priority of one (of) application (s) of (7) ....... patent ----------------------------------- ---------------- registered (s) isi (8) auxJE.tats-Uni.s ..... d., _ Améx.ique le (9) .... ......... 9 ...... September ...... 198.6 _________________________________________________________________________________________.__ under N ° (10) 9 Q..5 ..... 2.1.1 _________________________________________________________________________________________________________________... __________________________ on behalf of (11) ... s ...... inventors ______________________________________________________________ ^ __________________ elect (elect) domicile for him (her) and, if designated, for his representative, in Luxembourg '_________ ...... ..................................... 3.5., ....... bQulev.ard_ .RQyal ________________________________________________________ (12) soliir ite (s) the issuance of a patent for the subject described and represented in the abovementioned appendices, with postponement of this grant to ................... ..................................6 months. (13)

Lp-loaner / agent: ___________________________________________________________________________________-. . (14) / 1 Π. Deposit Minutes

The above patent application has been filed with the Ministry of the Economy and the Middle Classes, Serving Property MeDeetCeiJe ^ ptixernbourg, dated: September 9, 1987 ft-- Λ \ Pr. The Minister of Economy and Middle Classes, \ = if pd

jÿJ The head of the service ^ œ intellectual property, / '"" EXPLANATIONS RELATING TO THE FORMULA £ Î5rrÊPÔr ~! J / ”; . 52.689 CLAIM OF PRIORITY ✓ ’of the patent application / §IK In the United States of America

Of 9 September 1986 (No. '905.211) Brief Description filed in support of a request for

PATENT

at

Luxembourg

in the name of: COLGATE-PALMOLIVE COMPANY

NEW YORK, N.Y. 10022 (United States of America) for: "Non-aqueous liquid composition of non-ionic laundry detergent containing a persal bleach and a liquid organic bleach activator and process for its use." .1 *

NONAQUEOUS LIQUID DETERGENT COMPOSITION. NON-IONIC LAUNDRY CONTAINING A PERSEATED 'MONEY LAUNDERING AGENT' AND A LIQUID ORGANIC WHITENING ACTIVATOR AND

PROCESS FOR ITS USE.

The present invention relates to a nonaqueous liquid composition of nonionic laundry detergent containing a bleaching agent of the persal type and a liquid organic bleaching activator and a method for its use.

The compositions of the invention are stable against phase separation and gelling and are easy to pour and to use for cleaning soiled tissue.

Non-aqueous liquid deter ~ 1 gent compositions for heavy laundry are well known in the art.

For example, compositions of this type can comprise a liquid nonionic surfactant in which particles of a detergency builder are dispersed as indicated for example in US Patents 4,316,812, -3,630 929 and -4,264,466 and the British patents 1,205,711, 1,270,040 and 1,600,981.

25 Related patent applications by the applicant are: - patent application FR-86.04 468 filed on March 27, 1986, which describes a liquid composition of nonionic detergent for laundry containing a bleaching agent of the perborate type, a bleach activator and hydroxylamine sulfate as a bleach stabilizer and specifically a catalase inhibitor, "an enzyme found in natural body soils, which enzyme quickly breaks down peroxide, 2 I" # of hydrogen which is the component active bleaching of the perborate bleach; - Patent application FR-85.04 831 filed on March 29, 1985, which describes a nonaqueous liquid composition 05 of nonionic surfactant detergent comprising a suspension of tfh adjuvant detergency salt and containing a nonionic surfactant with acid termination (eg, the reaction product of a nonionic surfactant and succinic anhydride) to improve the dispersibility of the composition in a machine. automatic washing; - patent application FR-85.19 510 filed on December 31, 1985, which describes a nonaqueous liquid composition of nonionic surfactant detergent comprising a suspension of a detergency builder salt and containing a monoalkyl ether of alkylene glycol as agent regulating viscosity and gelation to improve the dispersibility of the composition in an automatic washing machine; 20 - patent application 85-05 319 filed on April 9, 1985, which describes a nonaqueous liquid composition of nonionic surfactant comprising a suspension of an adjuvant detergency salt of the polyphosphate type and containing an ester of alkanol and phosphoric acid to improve the stability of the suspension against sedimentation during storage.

These applications relate to non-aqueous liquid compositions of non-ionic laundry detergent.

Liquid detergents are often considered to be more convenient to use than dry powder or particulate products, and therefore enjoy great favor with consumers.

They are easy to measure, quickly dissolved in washing water, can easily be applied in the form of concentrated solutions or dispersions to the regions attached to the clothes to be washed, do not form dust and generally are less bulky during storage. In addition, materials can be incorporated into liquid detergent compositions which do not resist drying operations without deterioration, the use of these materials often being desirable in the manufacture of particulate detergent products. Many advantages over solid or particulate solid products, liquid detergents often also have some inherent disadvantages which must be eliminated to provide acceptable commercial detergents. Thus, some of these products separate during storage and others separate by cooling and are not easy to repeat. In some cases, the viscosity of the product varies and it becomes either too thick to be poured, or so fluid that it looks like water. Some clear products become cloudy and others gel on standing.

The Applicant has studied the behavior of nonionic liquid surfactant systems in which a particulate matter is in suspension. The non-aqueous liquid detergent compositions supplemented with a detergency builder and the problem of sedimentation of the suspended detergency builder and other laundry additives as well as the gelation problem associated with Non-ionic surfactants have aroused particular interest. These factors influence, for example, the stability, the ease of flow and the dispersibility of the product.

It is known that one of the major problems of liquid laundry detergents, added with a detergency builder, is their physical stability. This problem arises from the fact that the density of the solid particles dispersed in the nonionic liquid surfactant 4 * f *, is greater than the density of the liquid surfactant.

Therefore, the dispersed particles tend to sediment. There are two basic solutions for solving the sedimentation problem: increasing the viscosity of nonionic liquids or reducing the size of the dispersed solid particles.

It is known that suspensions can be stabilized against sedimentation by the addition of thickening agents or mineral or organic dispersants, such as for example very high surface area mineral materials such as silica and finely divided clays, etc. ., organic thickeners, such as cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc. However, this increase in the viscosity of the suspension is naturally limited *, since it is * necessary that the liquid suspension is easy to pour and fluid even at low temperature. In addition, these additives do not contribute to the cleaning performance of the composition.

Grinding to reduce the size of the particles provides the following advantages: 1. The specific surface area of the dispersed particles is increased and, consequently, the wetting of the particles by the nonaqueous vehicle (nonionic liquid) is proportionally improved; 2. The average distance between the dispersed particles is reduced, which proportionally increases the particle-particle interaction. Each of these effects contributes to increasing the gel strength at rest and the flow stress of the suspension, while simultaneously grinding significantly reduces the plastic viscosity.

The flow stress is by definition the minimum stress necessary to cause plastic deformation (flow) of the suspension. Thus, if the yoke considers the suspension as a loose network of dispersed particles, if the applied stress is less than the flow stress, the suspension behaves like an elastic gel and no plastic flow occurs. . As soon as the flow stress is exceeded, the network breaks at certain points and the sample begins to flow, but with a very high apparent viscosity. If the shear stress is much greater than the flow stress, the pigments exhibit partial deflocculation by shear and the apparent viscosity decreases. Finally, if the shear stress is much greater than the flow stress, the dispersed particles exhibit deflocculation by complete shear and the apparent viscosity is very low, as if there was no interaction between the particles.

Thus, the higher the flow stress of the suspension, the higher the apparent viscosity at low shear rate and the better the physical stability of the product against sedimentation.

In addition to the problem of sedimentation or phase separation, non-aqueous liquid laundry detergents based on non-ionic liquid surfactants have the disadvantage that non-ionic agents tend to gel when add to cold water. This is a particularly serious problem in the ordinary use of household automatic washing machines in Europe where the user places the detergent composition in a laundry unit. dispenser (for example a dispenser drawer) of the machine. During the operation of the machine, the detergent * of the dispenser is transported by a stream of cold water * into the main volume of the washing solution. In particular, during the winter months, when the detergent composition and the feed water of the dispenser are particularly cold, the screw "cosity of the detergent increases strongly and a gel is formed. As a result, part of the composition is not completely drawn out of the dispenser during the operation of the machine and a deposit of composition accumulates with the repetition of the washing cycles, which ultimately requires that the user rinse the 10 hot water dispenser.

The gelation phenomenon can also be a problem when it is desired to wash with cold water as this may not be recommended for certain synthetic and delicate fabrics or fabrics which may shrink in lukewarm or hot water.

The tendency to gel in storage of concentrated detergent compositions is exacerbated by storing the compositions in an unheated area or by transporting the compositions during the winter months in unheated transport vehicles.

Partial solutions to the gel problem of aqueous compositions, essentially devoid of detergency builders, have been proposed and include, for example, dilution of the liquid nonionic agent with certain viscosity adjusting solvents and inhibiting agents gelation, such as lower alkanols such as ethyl alcohol (see US Pat. No. 3,953,380), alkali metal formates and adipates (see US Patent 4,368 30,147), hexylene glycol, polyethylene glycol, etc. and modification and optimization of the nonionic structure. An example of modification of nonionic surfactants having a particularly good result is the acidification of the terminal hydroxyl moiety of the nonionic molecule. The advantages of introducing a carboxylic acid at the end of the nonionic agent 7 comprennent include the inhibition of, gelling by dilution, the lowering of the pour point of the nonionic agent and the formation of an anionic terisactive agent during neutralization in the washing liquid. Optimization of the nonionic structure focused mainly on the chain length of the hydrophobic-lipophilic moiety and the number and composition of the alkylene oxide (eg ethylene oxide) units of the hydrophilic moiety. For example, it has been found that a fatty alcohol ethoxylated with 8 moles of ethylene oxide exhibits only a limited tendency to gel.

Improvements in bleaching properties and in the stability and inhibition of gelation of nonaqueous liquid tissue treatment compositions containing a bleaching agent and a bleaching activator are desired.

According to the invention, a highly concentrated and stable non-aqueous liquid detergent composition is prepared containing a bleaching compound of the persal type and a liquid organic compound as a bleach activator. A preferred parsley bleaching compound is monohydric sodium perborate and a liquid organic compound constituting a preferred bleaching enhancer is ethylidene benzoate acetate. The liquid organic compound constituting the bleach activator is used to replace the conventionally used solid bleach activators, such as tetracetylethylenediamine (TAED) 30 and thus reduce the dry matter content of the concentrated detergent composition and improve the ease of flow. and the dispersibility of the composition.

. The system of bleach-type bleach and bleach activator consisting of an organic liquid of the invention can be used in adjuvant salt compositions for detergents rich or ♦ 8 low in phosphate.

To improve the viscosity characteristics of the composition, an acid-terminated nonionic surfactant can be added. To further improve the viscosity characteristics of the composition and the storage properties of the composition, it is possible to add to it viscosity improving agents and antifreezers, such as monoalkyl ethers of alkylene glycol and an agent. antisedimentation, such as an alkanol ester of phosphoric acid. In a preferred embodiment of the invention, the detergent composition contains as a bleaching agent for sodium perborate monohydrate, as a bleaching activator for benzoate-ethylidene acetate, a nonionic acid-active surfactant , a monoalkyl ether of alkylene glycol and an alkanol ester of phosphoric acid as an anti-sedimentation stabilizing agent.

The peroxygen bleaching compounds conventionally used, such as perborate, percar-bonate, perphosphate and sodium persulfate, can be used as bleaching agents.

In one embodiment of the invention, the detergency builder components of the composition can be ground to a particle size of less than 100 microns, for example less than 40 microns and preferably less than 10 microns to further improve stability of the suspension of the detergency builder components in the liquid nonionic surfactant detergent.

In addition, other ingredients can be added to the composition, such as anti-fouling agents, sequestering agents, anti-foaming agents, optical brighteners, enzymes, anti-redeposition agents, perfumes and colorants.

According to one of its aspects, therefore, the invention provides a liquid composition for coarse detergent 9 composed of a suspension of a peroxygen bleaching compound and a detergency builder salt, for example a phosphate builder salt in a liquid nonionic surfactant, this composition containing as bleach activator an effective amount of a liquid organic bleach activator compound such as ethylidene benzoate acetate.

In another aspect, the invention provides a concentrated liquid detergent composition for coarse laundry which has good bleaching properties. low temperature, is stable, does not sediment during storage and does not gel during storage or use. The liquid compositions of the invention are easy to pour, measure and introduce into the washing machine and are easily dispersible in water.

In yet another aspect, the invention provides a method for pouring a nonionic liquid laundry detergent composition into and / or with cold water without gelation occurring. In particular, the invention provides a method of filling a container with a nonaqueous liquid detergent composition for laundry, the detergent of which is composed, at least predominantly, of a liquid nonionic surfactant and to introduce the composition of the container 25 into an aqueous washing bath, a stream of unheated water being directed to the composition for this so that the stream of water carries it into the washing bath.

The use of the bleach activating liquid organic compound in the composition instead of the solid bleach activator reduces the problem of sedimentation of the dispersed particles and makes the composition easier to pour.

The replacement of prior art solid activators, such as TAED, with a liquid organic bleach activator reduces the total dry matter content of the composition and transforms the bleach activator into a liquid form dispersed in which it can react more easily with the Persian-type bleaching compound !.

The nonaqueous liquid compositions centered on non-ionic surfactant detergent for laundry of the invention have the advantage of being stable, of not sedimenting during storage and of not gelling during storage. easy to pour, measure and put into machine.

10 wash clothes and are easily dispersible in water.

An object of the invention is to provide a stable, nonaqueous liquid composition of a non-ionic detergent for coarse laundry containing a bleaching compound of the persel type and an activating compound of liquid organic bleaching, at least one viscosity adjusting agent. and anti-gelling agent, an anti-sedimentation stabilizing agent and an anionic adjuvant phosphate detergency salt suspended in a nonionic surfactant.

Another object of the invention is to provide liquid tissue treatment compositions which have good bleaching properties at low temperature, which are suspensions of mineral particles insoluble in a non-aqueous liquid and which are established during storage, easy to pour and dispersible in cold, lukewarm or hot water.

Another object of the invention is to prepare non-aqueous liquid compositions of non-Monique surfactant for heavy laundry. strong addition of detergency builder which can be poured at all temperatures and which can be repeatedly dispensed from the dispensing unit of the machines. wash European type automatic laundry without fouling or clogging the dispenser itself during the winter months.

»11 '*

A specific object of the invention is to provide stable, non-gelling suspensions of a nonaqueous liquid composition of nonionic detergent for heavy laundry added with a detergency builder, 05 which comprises a bleaching compound of the persel type and includes an effective amount of a liquid organic bleach activator compound.

These objects of the invention as well as others will appear on reading the following detailed description of preferred embodiments which are generally achieved by preparation of a detergent composition comprising an aqueous liquid nonionic surfactant, a parsley-type bleaching compound and a liquid organic activator of a parsley-type bleaching agent, said composition comprising mineral or organic tissue treatment additives, for example viscosity-enhancing agents and one or more antifreeze agents , anti-scaling, pH adjustment, anti-foaming agents, optical brighteners, enzymes, anti-deposition agents, perfumes, dyes and coloring pigments.

The invention will now be described in detail.

Parsley-type bleaching compounds

The nonaqueous liquid detergent nonionic detergent compositions of the invention contain a parsley-type bleaching compound and a liquid organic bleaching activator as essential ingredients of the composition.

Persal bleaches are well known in the art, are dispersed as solids in the non-ionic surfactant, and are readily soluble by adding the detergent composition to the aqueous wash. Persal type compounds or oxygenated bleaches are per-compounds which release hydrogen peroxide in aqueous solution. Preferred examples include sodium perborates, per- carbonates and perph.ospha.tes and potassium monopersulfa-te, perbora ~ tes are particularly preferred, especially sodium perborate monohydrate.

Hydrogen peroxide and the precursors which release hydrogen peroxide are good oxidizing agents for removing stains from tissues, in particular stains from wine, tea, coffee, cocoa, fruit, etc. Hydrogen peroxide and its precursors have generally been shown to whiten quickly and with better efficacy. a relatively high temperature, for example around 80 to 100 ° C.

To take advantage of effective detergents at. low temperature and wash cycles at. currently used for heat sensitive fabrics, the bleaching compound of the persal or peroxygen type is used in admixture with a bleach activator.

To date, solid bleach activators such as tetraacetylethylenedia-mine (TAED) have been used. The use of solid activators increases the solids content of the particles dispersed in the nonionic surfactant and requires that the solid bleach activators dissolve in the liquid aqueous bath before the activators can react with the compound. parsley bleaching.

Liquid organic bleach activators

According to the invention, liquid and limpid liquid organic bleach activating compounds are used to activate the bleaching compound of the persal type.

Since the organic bleach activators are liquid, they readily disperse in the nonionic liquid surfactant and, because the organic bleach activators are liquid, they react more easily with the bleaching agents. per salt type in the aqueous washing bath. The addition of liquid organic bleach activating compounds can lower the effective action temperature. bleaches of type 05 peroxide at values as low as 3Ö to. 40 ° C,

The preferred organic liquid bleach activating compounds correspond to the general formula:

II

/ ° "c - R2

Rl-CH <f 0 - C - Κ Ι 15 0 in which Rlf R2 and R3 are hydrocarbon radicals. R ^, R2 and R ^ may each independently be C1-C12 alkyl, for example C1-C2 alkyl such as C1-C2 alkyl; an aromatic radical, for example phenyl, and an aromatic (lower) alkyl, such as phenyl substituted with C 1 -C 4 alkyl; and a heterocyclic in to which the hetero atom is oxygen, nitrogen or sulfur, such as a radical derived from furan, tetrahydrofuran, thiophene, tetrahydrothiophene, oxazine, pyridine, pyrrolidine and pyrrolidone.

In the preferred embodiment R ^ is C 1 -C 4 alkyl, preferably CH3, R2 is C 1 -C 4 alkyl, preferably CH3, and R 3 is phenyl or phenyl substituted with 1 I 3 methyl groups, preferably phenyl or heptanoyl, the compound then being heptanqate-ethylidene acetate, octanoate-ethylidene acetate or dodecanoate-ethylidene acetate. · Cha-35 none of these compounds gives good results but heptanate is the best, probably because the hydrophilic-lipophilic balance is suitable for. 1 adsorption on the tissues and that the hydrophilicity remains sufficient to allow the reaction with hydrogen peroxide.

The preferred liquid organic bleaching agent 05 is ethylidene benzoate acetate which is a clear, fluid liquid which is readily available commercially.

Small amounts of the liquid organic bleach activating compound, such as ethylidene berizoate-ace-10, are sufficient to activate the peroxygen bleaching compound. For example, based on the total weight of the nonionic liquid surfactant composition, suitable proportions of ethylidene benzoate acetate are in the range of about 15% to about 15%, preferably about 1% to about 8.0% and better about 2% to 6%.

Usually, the bleach activator interacts with the peroxygen compound to form a bleaching agent of the peroxyaci-20 type in the wash water. It is preferred to incorporate a sequestering agent having a strong complexing power to inhibit any undesirable reaction between such a peroxyacid and hydrogen peroxide in the washing solution in the presence of metal ions.

Suitable sequestering agents for this purpose include the sodium salts of nitrilo-triacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DETPA), diethylenetriaminepentamethylenophosphonic acid (DTPMP) sold under the trade name Dequest 2066; and ethylenediaminetetramethy-lenephosphonic acid (EDITEMPA). The sequestering agents can be used individually or as a mixture.

To avoid the loss of peroxide-type bleach, for example sodium perborate, resulting from decomposition caused by enzymes; such as the enzyme catalase, the compositions may further contain an enzyme inhibitor, ie a compound capable of inhibiting the decomposition caused by the enzymes of the peroxide-type bleaching agent. Suitable inhibitor compounds are described in US Patent 3,606,990.

As a particularly useful inhibitor, hydroxylamine sulfate and other water-soluble salts of hydroxylamine may be mentioned.

In one embodiment of the nonaqueous compositions of the invention, the proportions of inhibitory hydroxylamine salts can be as low as about 0.01-0.4%. In general, however, suitable proportions of enzyme inhibitors can reach about 15%, for example 0.1-10% of the weight of the composition.

Stabilizers can also be added to the composition, such as, for example, an acidic organic phosphorus compound having an-acide acid group, such as a partial ester of phosphorous acid and an alkanol.

Non-ionic surfactant detergents can be supplemented with adjuvant salts for detergents of the polyphosphate type or with a low polyphosphate content.

Nonionic surfactant detergent The synthetic nonionic organic detergents employed in the practice of the invention can be selected from a wide variety of known compounds.

As is well known, non-ionic synthetic organic detergents are characterized by the presence of a hydrophobic organic group and a hydrophilic organic group and are typically produced by the condensation of an aliphatic or aikylaromatic hydrophobic organic compound with ethylene oxide (hydrophilic in nature). In practice, any hydrophobic compound having a carboxy, hydroxy, amido or amino group can be condensed with free hydrogen attached to nitrogen with ethylene oxide or with its polyhydration product, polyethylene glycol to form non-ionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to ensure the desired balance between the hydrophobic and hydrophilic groups. Typical suitable nonionic surfactants are those described in US Patents 4,316,812 and 3,630,929.

Usually, nonionic detergents are lipophilic compounds polyalkoxylated by lower alkoxy in which the desired hydrophilic-lipophilic balance is obtained by addition of a hydrophilic lower polyalkoxy group to a lipophilic moiety. A preferred category of the nonionic detergents employed consists of the higher alkanols polyalkoxy-injured by lower alkoxy whose alkanol has from 9 to 18 carbon atoms and the number of moles of lower alkylene oxide (having 2 or 3 carbon atoms) 20 is from 3 to 12. Among these materials, it is preferable to use those in which the higher alkanol is a fatty alcohol higher than 9 to 11 or 12 to 15 carbon atoms and which contains 5 to 8 or 5 to 9 lower alkoxy groups per mole. Preferably, the lower alkoxy is a methoxy, but in some cases it may be desirable to mix it with a propoxy, the latter, when present, often being in a minor proportion (less than 50%).

Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, for example Neodol 25-7 and Neodol 23-6.5, these products being manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 carbon atoms with about 7 moles of ethylene oxide 17 , and the second is a corresponding mixture in which the number of carbon atoms of the higher fatty alcohol is from 12 to 13 'and the number of the oxy-y groups of ethylene present is on average about 6.5 .

05 Higher alcohols are primary alkanols.

Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9 which are both linear secondary alcohol ethoxylates manufactured by Union Carbide Corp. The first is a mixed product of ethoxylation of a linear secondary alkanol having 11 to 15 carbon atoms with 7 moles of ethylene oxide and the second is a similar product but in which 9 moles of ethylene oxide have reacted.

As a component of the nonionic detergent, there may also be used in the present composition higher molecular weight nonionic agents, such as Neodol 45-11, which are similar condensation products of ethylene oxide. al-20 higher fatty cools, the higher fatty alcohol having 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are also manufactured by Shell Chemical Company.

Other useful nonionic agents are represented by the commercially well known category of nonionic agents sold under the trademark Plurafac. Plurafacs are products of the reaction of a higher linear alcohol and a mixture of ethylene and propylene oxides containing a mixed chain of ethylene oxide and propylene oxide terminated by a hydroxyl group. . Examples include the products which are: (A) a C 1 -C 4 fatty alcohol condensed with 6 mol of ethylene oxide and 3 moles of propylene oxide, (B) a fatty alcohol in C ^ -C ^ condensed with 7 mol— • ^ propylene oxide and 4 moles of ethylene oxide, (C) a fatty alcohol in C ^ -C ^ condensed with 5 ma * · les propylene oxide and 10 moles of ethylene oxide, and 05 (D) a l / l mixture of products (B) and (C).

Another group of liquid nonionic agents is constituted by those sold by Shell Chemical Company under the trademark Dobanol: Dobanol 91-5 is an ethoxylated fatty alcohol 10 with on average 5 moles of ethylene oxide and the Dobanol 25-7 is a C12 ~ C15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

In polyalkoxylated higher alkanols with preferred lower alkoxy, to obtain the best balance of hydrophilic and lipophilic moieties, the number of lower alkoxy groups is generally 40 to 100% of the number of carbon atoms of the higher alcohol, preferably 40 to 60% and the nonionic detergent preferably contains at least 50% of this higher (lower) alkanol polyalkoxy. Higher molecular weight alkanols and various other normally solid detergents and nonionic surfactants can contribute to gelation of the liquid detergent and therefore are avoided or limited in the present compositions, although minor proportions of these can be used due to their cleaning properties, etc. With regard to preferred and less preferred nonionic detergents, the alkyl groups present therein are generally linear, although branching may be tolerated, for example on the carbon atom neighboring or distant from two carbon carbons end of the straight chain and opposite of the ethoxy chain, if such a branched alkyl has not more than 3 carbon atoms. Normally, the proportion of carbon atoms in such a branched configuration is minor and rarely exceeds 20% of the total carbon content of the alkyl. Likewise, though. linear alkyls which are united at the end with the ethylene oxide chains are very much preferred and which are considered to provide the best combination of detergency, biodegradability and non-gelling characteristics, a median or secondary union to ethylene oxide in the chain may occur. It generally only occurs in a minor proportion of such alkyls, generally less than 20% but, as in the case of the Tergitol mentioned, it can be higher. Also, when propylene oxide is present in the lower alkylene oxide chain, the proportion is generally less than 20% and preferably less than 10%.

When larger proportions of non-alkoxylated alkanols, polyalkoxylated alkoxy alcohols containing propylene oxide and a detergent with a poorer hydrophilic-lipophilic balance than that used, are employed. has been mentioned above, and when other nonionic detergents are used instead of the preferred nonionic detergents mentioned herein, the product obtained may not have detergency, stability, viscosity and non-detergency properties. gelation as good as that of the preferred compositions, but the use of the viscosity control and gelation compounds of the invention may also improve the detergents which are based on such nonionic agents. In some cases, such as when using a higher alkanol polyalkoxylated by lower alkoxy having a higher molecular weight, often due to its detergency, its proportion can be adjusted or limited according to the results of ordinary experiments in order to to obtain the desired detergency while preserving a product which does not freeze, does not have the desired viscosity. It has also been found that it is only rarely necessary to use higher molecular weight nonionic agents due to their detergent properties, since the preferred nonionic agents described herein are excellent detergents and allow more to obtain the desired viscosity of the liquid detergent without gelation at low temperatures.

Another useful group of nonionic surfactants is the "Surfactant T" series of nonionic agents provided by British Petroleum. The nonionic agents Surfactant T are obtained by ethoxy-lation of C13 secondary fatty alcohols with a narrow distribution of ethylene oxide. Surfactant T5 has an average of 5 moles of ethylene oxide; Surfactant T7 on average 7 moles of ethylene oxide; Surfactant T9 on average 9 moles of ethylene oxide and Surfactant T12 on average 12 moles of ethylene oxide per mole of C13 secondary fatty alcohol.

In the compositions of the invention, the preferred nonionic surfactants include secondary fatty alcohols having relatively narrow contents of ethylene oxide in the range of about 7 to 9 moles and fatty alcohols in Cg to ethoxy-25 with about 5 to 6 moles of ethylene oxide.

Mixtures of two or more of the liquid nonionic surfactants can be used, and in some cases the use of such mixtures has advantages.

30 Acid-terminated nonionic surfactants

The viscosity and gel properties of liquid detergent compositions can be improved by incorporating an effective amount of an acid-terminated liquid nonionic surfactant.

The acid-terminated nonionic surfactants consist of a nonionic surfactant 21 which has been modified so that a free hydroxyl group is converted to a moiety having a free carboxy group, such as a ester or partial ester of a nonionic surfactant and a po-05 lycarboxylic acid or anhydride.

As described in patent application FR-85 3 05 319 filed on April 9, 1985 by the Applicant, non-ionic surfactants modified by a free carboxyl group, which can generally be characterized as polyethercarboxylic acids, lower the temperature at which the liquid nonionic agent forms a gel with water.

The addition of acid-terminated nonionic surfactants to the liquid nonionic surfactant contributes to the distribution of the composition, i.e., its ease of flow, and lowers the temperature at which liquid nonionic surfactants gel with water. The acid-terminated nonionic surfactant reacts in the washing machine water with the alkalinity of the detergent dispersant builder salt phase of the detergent composition and acts as an effective anionic surfactant.

Specific examples include the hemi-esters of nonionic surfactant (A) with succinic anhydride, the ester or hemiester of Doba-nol 25-7 with suadnic anhydride. and the ester or hemiester of Dobanol 91-5 with succinic anhydride. Instead of succinic anhydride, it is possible to use other polycarboxylic acids or anhydrides such as maleic acid, maleic acid anhydride, glutaric acid, malonic acid, phthalic acid, phthalic anhydride, citric acid and the like.

Nonionic surfactants can be prepared as follows. acid ending:

Acid-terminated product (A). 400 g 4 22 of non-ionic surfactant (A) are mixed, · a non-ionic surfactant, which is an alkanol in which we have alkoxylated to introduce six units of ethylene oxide and three units of propylene oxide by alkanol unit, ° 5 with 32 g of succinic anhydride and heating for 7 hours at 100 ° C. The mixture is cooled and filtered to remove it. unreacted succinic material. Infrared analysis indicates that about half of the nonionic surfactant has been converted to the corresponding acid hemiester.

Dobanol 25-7 with acid termination. 522 g of the nonionic surfactant Dobanol 25-7 are mixed, which is a product of the ethoxylation of a C 2 -C 15 alkanol and has approximately 7 units of ethylene oxide per molecule. alkanol, with 100 g of succinic anhydride and 0.1 g of pyridine (which acts as an esterification catalyst) and heated to 260 ° C for 2 hours, cooled and filtered to remove the succinic material n not reacted. · Infrared analysis indicates that almost all of the free hydroxyls of the surfactant have reacted.

Acid-terminated Dobanol 91-5. 1,000 g of the nonionic surfactant Dobanol 91-5, which is an ethoxylation product of a C 25 to 25 alkanol and has about 5 ethylene oxide units per alkanol molecule, are mixed. , with 265 g of succinic anhydride and 0.1 g of pyridine as catalyst and heated to 260 ° C for 2 hours, cooled and filtered to remove the unreacted succinic material. Infrared analysis indicates that almost all of the free hydroxyls of the surfactant have reacted.

Other esterification catalysts, such as an alkali metal alcoholate (such as sodium methylate) can be used in place of or mixed with pyridine.

The acidic polyether compound, that is to say the 1 i ’23 gent nonionic surfactant with acid termination, is preferably added in the dissolved state to house nonionic surfactant.

Adjuvant detergency salts · 05 The liquid non-aqueous nonionic surfactant used in the compositions of the invention contains, in dispersion and suspension, fine particles of mineral salts and / or organic detergency adjuvants.

The detergent compositions of the invention include water soluble and / or water insoluble builder salts. The water-soluble alkaline mineral salts detergency builders, which can be used alone with the detergent compound or in admixture with other detergency builders, are carbonates, bicarbonates, borates, phosphates, polyphosphates and alkali metal silicates. (It is also possible to use ammonium or substituted ammonium salts). Specific examples of such salts are sodium tri polyphosphate, sodium carbonate, sodium t-traborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tri polyphosphate, 1 ' sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and diorthophos-phate and potassium bicarbonate. Particular preference is given to sodium tripolyphosphate (TPP).

Since the compositions of the invention are generally very concentrated and can therefore be used at relatively low doses, it is desirable to add any detergency builder phosphate (such as sodium tripolyphosphate) to a detergency builder auxiliary, such as a lower polycarboxylic acid or a polymeric carboxylic acid having a strong calcium binding capacity to inhibit incrustation which could otherwise occur by formation of an insoluble calcium phosphate. Suitable lower polycarboxylic acids include the alkali metal salts of lower polycarboxylic acids, preferably the sodium and potassium salts. Suitable lower polycarboxylic acids have 2 to 4 carboxylic acid groups. The preferred so-05 dium and potassium salts of the lower polycarboxylic acids are the citric and tartaric acid salts. The sodium salts of citric acid are particularly preferred, in particular trisodium citrate.

Monosodium and disodium citrates can also be used. Monosodium and disodium salts of tartaric acid can also be used. The alkali metal salts of lower polycarboxylic acids are salts constituting particularly good detergent builders; due to their strong calcium and magnesium binding capacity * they inhibit the encrustation which would otherwise cause the formation of insoluble calcium and magnesium salts.

To obtain a phosphate-free detergent composition, polyphosphate 20 can be completely replaced by one or more auxiliary detergency builders.

Other organic detergency builders are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their alkali metal salts. More particularly, these adjuvant detergency salts can form a copolymer, which is the product of the reaction of approximately equal molar amounts of methacrylic acid and moleic anhydride, which has been completely neutralized to form its sodium salt. The detergency builder is marketed under the trade name Sokalan CP5. This detergency builder is used, when used even in small amounts, to inhibit encrustation.

Examples of other sequestering alkaline organic salts with detergency builders which can be used with the detergent builders or in admixture with other organic detergency builders and f V. ·, 25 minerals are the aminopolycarboxylates of alkali metal, ammonium or substituted ammonium such as sodium and potassium ethylenedia-minetetraacetates (EDTA), sodium and potassium nitrilotriacetates (NTA) and 05 N- (2 -hydroxyethyl) nitrilodiacetates of triethanolammonium. Mixed salts made up of these aminopolycarboxylates are also suitable.

Other suitable organic type detergency builders include carboxymethyl succinates, tartronates and glycolates. Polyacetal-carbo-xylates are particularly useful. Polyacetal carboxylates and their use in detergent compositions are described in patent application FR-86 11 852 filed on August 19, 1986 by the Applicant and in US patents 4,144,226, -4,315,092 and -4,146 495.

The alkali metal silicates are useful detergent builder salts which also function to adjust or limit the pH and to make the composition anticorrosive to the elements of washing machines. Sodium silicates having Na20 / SiO2 ratios of 1.6 / 1 to 1 / 3.2, in particular about 1/2 to 1 / 2.8 are preferred. Potassium silicates having the same ratios can be used.

Other typical detergency builders include, for example, those described in US Patents 4,316,812, -4,264,466 and -3,630,929. The mineral detergent builders can be used with the surfactant detergent compound. active non-ionic or in admixture with other mineral adjuvant salts for detergent or organic adjuvant detergent salts.

Zeolites consisting of crystalline and amorphous water-insoluble α-luminosilicate can be used. The zeolites generally respond to the formula: 35 (M20) x * CA12 ° 3 V (SiCV z * wH2 ° i

'I

26 in which x is 1, y is 0.8 to 1.2 and preferably 1, z is 1.5 to 3.5 or more and preferably 2 to 3 and w is 0 to 9, preferably from 2.5 to 6 and M is preferably sodium. A typical zeolite is of type 05 A or has a similar structure, type 4A being particularly preferred. Preferred aluminosilicates have calcium ion exchange capacities of about 200 milli-equivalents per gram or more, for example 400 mEq / g;

Various crystalline zeolites (that is, aluminosilica-10 tes) which can be used are described in patent GB-1,504,168, patent US-4,409,136 and patents CA-1,072,835 and -1,087,477. An example of amorphous zeolites useful here appears in patent BE-835,351.

Other materials such as clays, particularly of the water insoluble type, may be useful additives in the compositions of the invention. Bentonite is particularly useful. This material consists mainly of montmorillonite which is a hydrated aluminosilicate of which approximately 1/6 of the aluminum atoms can be replaced by magnesium atoms and to which variable quantities of hydrogen, sodium, potassium, calcium, etc. . can be loosely combined. Bentonite, in its most purified form (that is to say free of any sandstone, sand, etc.) suitable for detergents, contains at least 50% of montmorillonite and its cation exchange capacity is therefore at least about 50 to 75 mEq / 100 g of bentonite. Particularly preferred bentonites are the bentonites from Wyoming or the western region of the United States sold under the name of Thixo-jel 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textiles such as described in patents GB-401,413 and -461,221.

35 · Adjustment agents for: "viscosity and anti-freeze 1 flours Incorporation into the detergent composition 27 4 'an effective amount 4th ampholyte compounds, which function as 4th adjustment agents 4th viscosity and 4'inhibition 4th gelation 4th non-ionic surfactant, significantly improves the 4th storage properties of the composition. 4'adjusting agents 4th viscosity and 4'inhibition 4th gelation lower the temperature to which the nonionic surfactant forms a gel when added to water 4. These agents 4 adjust the viscosity and inhibit 4 the gelation can for example be 4th ampholyte compounds 4th type lower monoalkyl ether 4'oxy-4e 4'alkylene 4th low molecular weight. It can be considered that the ampholyte compounds have a chemical structure similar to that of the nonionic surfactants constituted by liquids. ethoxylated and / or propoxylated fatty alcohol but have 4 hy4rocarbon chains relatively short (C_ to C_) and low oxy4e content

Δ O

4'ethylene (about 2 to 6 oxy4 groups 4'ethylene per molecule).

The suitable ampholyte compounds are represented by the following general formula: R2

X I

25 R10 (CHCH20) nH

2 in which R is a C 1 -C 6 alkyl group, R is hydrogen or methyl and n is a number which has an average value of 4 to about 1 to 6.

In particular, the compounds are lower monoalkyl ethers (C2 to C8) lower alkylene glycol (C2 to C8).

More particularly, the compounds are 4th monoalkyl ethers lower than Cg) 4th mono-, 4i- or lower trialkylene glycol (C2 è Çg).

Specific examples of the suitable ampholyte compounds include: 28 - the ethylene glycol monoethyl ether C2H5r-o- ch2ch2oh, - the diethylene glycol monobutyl ether C4Hg-0- (ch2ch2o) 2 h 05 - the monobutyl ether tetraethylene glycol C4H -0-CCH2CH20) .4H and - the monomethyl ether of dipropylene glycol ch3-o- (chch2o) 2h.

CH,

10 J

Particular preference is given to the diethylene glycol monobutyl ether.

The incorporation into the composition of the lower molecular weight lower alkylene glycol monoalkyl ether reduces the viscosity of the composition, so that it is easier to pour, improves sedimentation stability and improves the dispersibility of the composition when added to hot or cold water.

The compositions of the invention have improved viscosity and stability characteristics and remain stable and easy to pour at temperatures as low as about 5 ° C and below.

In one embodiment of the invention, a stabilizing agent which is an alkanol ester of phosphoric acid can be added to the composition.

Improvements in the stability of the composition can be achieved by incorporating a small effective amount of an acidic organic phosphorus compound having an acid group -POH, such as a partial ester, phosphorous acid and an alkanol. As described in patent application FR-85.05 319 filed on April 9, 1985 by the Applicant, the acidic organic phosphorus compound having an acid group -POH can increase the stability of the suspension of detergent builders in the surfactant non ionic liquid non t 29 aqueous. The acidic organic phosphorus compound can for example be a partial ester of phosphoric acid and of an alcohol such as an alkanol having a lipophilic character and containing for example more than 5 carbon-05 atoms, for example 8 to 20 carbon atoms.

A specific example is a partial ester of phosphoric acid and a C1-C6 alkanol (Em-piphos 5632 from Marchon); it consists of approximately 35% monoester and 65% diester.

The incorporation of very small quantities, for example 0.3% by weight, of the acidic organic phosphorus compound makes the suspension stable with respect to sedimentation at rest but still allows it to be poured although only for a low concentration of stabilizing sta-15, for example less than about 1%, its plastic viscosity generally decreases.

Other bleach activators can optionally be added to the composition; among them are bleach activators such as tetraacetylethylene diamine ("TAED") and pentaaceous-tylglucose, acetylsalicylic acid derivatives, alkyl- and alkenylsuccinic anhydrides, tetra-acetylglyco-urile ("TAGU" ) and their derivatives.

In addition to detergent builders, various other detergent additives may be present in the detergent product to provide it with desired additional functional or aesthetic properties. Thus, it is possible to incorporate into the composition minor amounts of suspending agents for smearing or anti-deposition, for example po-lyvinyl alcohol, fatty amides, sodium carboxymethylcellulose and hydroxypropylmethylcellulose. A preferred anti-redeposition agent is sodium carboxymethylcellulose having a CMC / MC ratio of 2/1 which is sold under the trade name Relatin DM 4050.

Small amounts of Duet 787, which is a laundry detergent scent supplied by International Flayors and Fragrances, Inc, Union Beach, N-J, can also be incorporated into the composition. 07735 (U, S, A.), Duet 787 can be added in proportions from 0 to.

05 3, preferably from 0.2 to 2.0, for example from 0.5 to 2%, such as 0.3 to 1.0% of the weight of the composition.

Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include the compositions based on stilbene, triazole and benzidine sulfone, in particular sulfonated substituted triazinylstilbene, naphtotriazostylbene sulfonated, benzidine sulfone, etc., the combinations of stilbene and triazole being particularly preferred. A preferred optical brightener is Stilbene Brightener N4 which is a dianilinodimorpholinostilbene polysulfonate.

Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelain, papain, trypsin and pepsin, as well as amylase-like enzymes, lipase-like enzymes, and mixtures thereof can be added. Preferred enzymes include a protease suspension, esperase suspension and amylase. A preferred enzyme is Esperse SL8 which is a proteolytic enzyme. Antifoaming agents, such as a silicon compound, such as Silicane L 7604, which is a polysiloxane, can also be added in small effective amounts.

Bactericides such as tetrachlorosalicyla-30 nilide and hexachlorophene, fungicides, dyes, pigments (water dispersible) preservatives, ultraviolet absorbents, anti-yellowing agents, such as sadic carboxymethylcellulose, pH modifiers and pH buffers, color-respecting bleaches, fragrances and dyes and whiteners such as 31 ·,.

'*; overseas blue can be used,.

In one embodiment of the invention, the stability of the adjuvant salts for detergent in the composition during storage and the dispersibility of the composition in water are improved by grinding and decreasing the particle size of the adjuvants. solid detergents less than 100 µm, preferably less than 40 µm and better still less than 10 µm. Additives for solid detergents, for example sodium tripo-10 lyphosphate (TPP), are generally supplied in particle sizes of about 100, 200 or 400 µm. The nonionic liquid surfactant phase may be mixed with the solid detergent builders before or after the crushing operation. In a preferred embodiment of the invention, the mixture of the surfactant liquid nonionic active ingredient and solid ingredients is subjected to attrition milling in which the particle sizes of the solid ingredients are reduced to less than about 20 µm, i.e. to an average particle size of 2 at 10 ^ im or even less (for example 1 jim). Preferably less than about 10% and in particular less than about 5% of all suspended particles have sizes greater than 10 µm. The compositions whose dispersed particles have such a reduced size exhibit an improvement in stability against; separation or sedimentation on storage. Addition of the acid-terminated nonionic surfactant can reduce the flow stress of these dispersions and contribute to the dispersibility of the dispersions without a corresponding decrease in the stability of the dispersions against sedimentation.

. In the grinding operation, it is preferred that the proportion of the solid ingredients is sufficiently high (for example at least about 40%, such as about 50%), for the solid particles to be 32%. mutual contact and are essentially not isolated from each other by the liquid nonionic surfactant. After the grinding stage / any residue of liquid nonionic surfactant can be added to the ground composition. Grinders which use balls (ball mills) or similar movable grinding elements have given very good results. It is therefore possible to use a discontinuous mill by laboratory attrition containing grinding balls 10 made of soapstone 8 mm in diameter. For an operation at.

on a larger scale, a continuous mill can be used containing grinding balls of 1 m or 1.5 m in diameter with a very small gap between a stator and a rotor operating at a relatively high speed (for example a CoBall); when using such a mill, it is desirable to pass the mixture of the nonionic surfactant and the solids first through a mill which does not perform such fine grinding (for example a colloid mill) to reduce the particle size to less than 100 µm (for example, about 40 µm) before the grinding stage to an average particle diameter of less than about 10 µm in the continuous ball mill.

In the preferred liquid laundry detergent compositions of the invention, the typical proportions (percentages by ratio ± to the total weight of the composition, unless otherwise indicated) of the ingredients are as follows: Nonionic surfactant detergent in the range 30 from about 10 to 60, such as 20 to 50%, for example about 30 to 40 I.

Viscosity improver, acid-terminated nonionic surfactant in a proportion in the range of about 0 to 20, such as 1 to 10%, for example about 2 to 5%.

Detergency builder such as tripolyphosphate 33 "r, sodium (tpp) in the range of about 10 to 60, such as 15 to 50%, for example about 25 to 35%.

Copolymer of acrylic acid and maleic anhydride, alkali metal salt, such as Sokalan CP5, anti-scaling agent 05 in the range of approximately 0 to 10, such as 1 to 8%, for example about 2 to 4 I.

Alkylene glycol monoalkyl ether, antifreeze agent in a proportion in the range of about 5 to 30, such as 5 to 20%, for example about 5 to 15%.

An alkanol ester of phosphoric acid, stabilizing agent, in the range of 0 to 2.0 or 0.1 to 1.0, such as 0.2 to 0.5%.

Persal type bleach in the game of about 5 to 30, such as 2 to 20, for example about 15 to 15%.

Liquid organic bleach activator compound, such as ethylidene benzoate-acetate, in the range of about 1 to 15, such as 1 to 8, for example about 2 to 6%.

20 Sequestering agent for the bleach, such as Dequest 2066 in the range of about 0 to 3.0, preferably 0.5 to 2.0%, such as about 0.50 to 1.25 %.

Anti-redeposition agent, such as Relatin Dîi 4050, in the range of about 0 to 4.0, preferably 0.5 to 25%, for example 0.5 to 1.5%.

Optical brightener in the range of about 0 to 2.0, preferably 0.05 to 1.0%, such as 0.15 to. 0.75% „

Enzymes in the game from about 0 to 3.0, preferably from 0.5 to. 2.0%, for example from 0.75 to 1.25%.

30 Perfume in the game of about 0 to 3.0, preferably 0.10 to 1.25%, such as 0.25 to 1.0%.

Various of the above additives can optionally be added to provide the desired function of the added materials.

The liquid organic bleach activator compound is preferably used with at least one of 34 monoalkyl monoethers or viscosity adjusting agents and nonionic acid-terminating surfactant antifreezers. In some cases ,, benefits can be obtained by employment to; both mono-05 alkylene glycol ethers and acid-terminated nonionic surfactants.

additives compatible with the main constituents of the detergent composition must be chosen. In the present description, as mentioned above, all the proportions and all the percentages relate to the weight of the complete composition unless otherwise indicated.

The nonaqueous liquid composition of concentrated nonionic detergent of the invention is easy to introduce into the washing machine.

According to one embodiment of the invention, a typical detergent composition is prepared using the ingredients indicated below:

20% by weight Non-ionic surfactant detergent or mixture 20-45

Viscosity improver, acid-terminated surfactant 0-20 25 Phosphate-type salt adjuvant for detergent 10-60

Anti-encrustation agent 0-10

Alkylene glycol monoalkyl ether, anti-gelling agent 5-15 30 Phosphoric acid alkanol ester, stabilizing agent 0-2.0

Anti-layering agent 0-4.0

Alkali metal perborate bleach 5-15 35 Liquid organic bleach activator compound, for example, benzoa- 1-ethyl acetate 1.0-8 ', 0

Bleach sequestering agent 0-3, 0

Perfume (Duet 787) 0-3.0 '05 Optical brightener 0.15-0.75

Enzymes 0.75-1.25

Perfume 0-3.0 'The invention is further illustrated by the following 10 examples.

EXAMPLE 1

A concentrated nonaqueous liquid composition of nonionic surfactant is prepared from the following ingredients in the amounts indicated.

% in weight

Non-ionic surfactant 37.0

Acid-terminated product of the reaction of Dobanol 91-5 with succinic anhydride 5.0

Sodium tripolyphosphate (TPP) 31.4

Diethylene glycol monobutyl ether, antifreeze agent 10.0 25 Phosphoric acid alkanol ester (Empiphos 5632) 0.3

Sodium perborate monohydrate, bleach 9.0

Benzoate-ethylidene acetate, whitening activator 4.5

Anti-layering agent (Relatin DM

4050) 1 1.0

Optical brightener (Tinopal ATSX) 0.2

Fragrance 0.6 35 Enzyme (Esperase) 1.0 100.0 36 1.

(X) Mëla, nge in a 2/1 CMC / MC ratio (carboxy-methylcellulose sodium and hydroxymethÿlcellulose.

The composition is ground for about 1.05 hours to reduce the particle size of the detergent builder salts in suspension to less than 40 µm. It is found that the detergent composition is stable and does not gel on storage, is easy to redisperse in water and has good bleaching properties.

A nonaqueous liquid composition of nonionic surfactant concentrated at. from the following ingredients in the quantities indicated.

15% by weight

Surfactant, product D 13.5

Surfactant T7 10.0

Surfactant T9 10.0 20 Acid-terminated product of the reaction of Dobanol 91-5 with succinic anhydride 5.0

Sodium tripolyphosphate (TPP) 29.6

Anti-scaling agent (Sokalan 25 CP5) 4.0

Diethylene glycol monobutyl ether, anti-gelling agent 10.0

Ester of alkanol and phosphoric acid (Empiphos 5632) 0.3 30 Sodium perborate monohydrate, bleach 9.0

Benzoate-ethylidene acetate, bleach activator 4,5

Bleach sequestering agent (Dequest 2066) 1.0

Anti-Layout Agent (Relation DM 4050) * 1.0 '. 37 '! I · 1 /

Optical brightener (Stilban) 0.5 '

Enzyme (Esperase suspension) 1.0

Duet 787 (2) 0/6 100.0 05 (1) Mixture in a CMC / MC DE 2/1 ratio of sodium carboxymethylcellulose and hydroxymetylcellulose, (2) Duet 787 is a fragrance from IFF, Inc .

The composition is ground for about 1 hour to reduce the particle size of the detergent builder salts to less than 40 µm. It is found that the detergent composition is stable and does not gel on storage and is easily dispersed in water.

15 The bleach is active at 40 ° C on wine stains and occasional black stains.

The compositions of Examples 1 and 2 can be prepared without grinding to a small particle size the detergent builder salts and solid suspended particles, but best results are obtained by grinding the composition to reduce the size of the solid particles. in suspension.

The detergency builder salts can be used as such or the detergency builder salts and the suspended solid particles can be ground or partially ground prior to mixing with the nonionic surfactant. The grinding can be carried out partly before mixing and completed after mixing or otherwise the entire grinding operation can be carried out after mixing with the liquid surfactant. Compositions containing a detergent builder and suspended solid particles having sizes less than 40 µm are preferred.

The system of the invention, consisting of the bleaching composition of the persal type and the activating compound of liquid organic bleaching, can also be 38.

used in non-ionic surfactant detergent compositions for dishwashing, scouring creams and other bleaching compositions.

05 Of course the above description is presented for illustrative purposes only and variations can be made without departing from the scope of the invention.

Claims (19)

39 1. • 1 ·, 4 "* \ 1. A detergent composition for the treatment of fabrics, comprising a liquid, non-ionic surfactant detergent, a peroxy-hindered mineral bleaching agent and a liquid organic bleaching activating compound. 2. Composition according to claim 1, characterized in that it comprises a viscosity regulating agent and anti-gelling agent. 3. Detergent composition according to claim 1, characterized in that it comprises at least one viscosity regulating and antifreeze agent chosen from the group consisting of a monoalkyl ether of alkylene glycol and a nonionic surfactant. - 15 only with an acid ending. 4. Composition according to claim l, characterized in that it comprises a suspension of an insoluble mineral salt detergency builder. 05 R2 R10 (CHCH90) H, i ^ Π 1 * 2 wherein R is a C1 to C6 alkyl group, R is hydrogen or methyl and n is a number 10 having an average value in the range of about 1 to 6, as an additive for inhibiting gelation in a proportion of at most about 5 to 30% by weight. 5. Composition according to claim 1, characterized in that the liquid organic compound activating bleaching corresponds to the general formula: 0 II 25 / ° "C R2 R. - CH ^ 1 \ 0. C - R, II o 30 in which R ^, R2 and R3 are hydrocarbon radicals, the hydrocarbon radicals being chosen so that the organic compound is liquid. \ 6. Composition according to claim 4, characterized in that the insoluble adjuvant mineral salt 35 (detergency I consists of 10 to 60% of a detergency adjuvant polyphos-phate., 40 F. ‘Ϊ́" · 7. detergent composition according to claim l, characterized in that it comprises one or more detergency adjuvants chosen from the group consisting of an anti-encrustation agent, a sequestering agent, an anti-redeposition agent, an optical brightener , enzymes and a fragrance. 8. Composition according to claim 1, characterized in that it comprises 10 to 60% of a nonionic liquid surfactant detergent. 9. Detergent composition according to claim 3, characterized in that it comprises 5 to 30% of a monoalkyl ether of alkylene glycol. 10. Composition according to claim 4, characterized in that the adjuvant mineral salt of detergency has a particle size of less than 40 JMU 11. Composition according to claim 1, characterized in that it contains approximately 0.1 to approximately 0.5% by weight, relative to the total composition, of an alkanol ester of phosphoric acid as stabilizing agent. anti-sedimentation. 12. Non-aqueous detergent composition for heavy laundry added with a detergency builder, which can be poured at high and low temperatures and which does not gel when mixed 25. cold water, the composition comprising: - at least one liquid nonionic surfactant in a proportion of about 10 to about 60% by weight; - At least one adjuvant mineral salt for detergent 30 suspended in the nonionic surfactant in a proportion of about 10 to about 60% by weight; - a peroxygenated mineral bleaching agent in a proportion of approximately 5 to 15 I; - ethylidene benzoate-acetute as activa, - bleaching agent in a proportion of about 1 to 8.0% i. 41 i, - an acid-terminated nonionic surfactant as an additive for inhibiting gelation in a proportion of about 0 to 20% by weight? and - a compound of formula 13. Detergent composition as claimed in claim 12, characterized in that it optionally contains one or more adjuvants for detergent chosen from the group consisting of an anti-encrustation agent, a sequestering agent, an anti-redeposition agent, an optical brightener, an enzyme and a fragrance. 14. A non-aqueous liquid detergent composition-20 for heavy laundry according to claim 12, characterized in that it comprises:% by weight Non-ionic surfactant in a proportion of about 20-50 25 Sodium tripolyphosphate (TPP) in a proportion of about 15-50 Copolymer of acrylic acid and maleic anhydride (sodium salt), in a proportion of about 1-8 20 Diethylene glycol monoalkyl ether in a proportion of about 5-20 Alkanol ester of phosphoric acid in a proportion of about 0.1-1.0 Sodium perborate monohydrate, bleach, in a proportion about 2-20; > 0 42 f Benzoate-ethylidene acetate, whitening activator, in a proportion of about 1-8 15 Sodium tripolyphosphate in a proportion of about 25-35 Copolymer of acrylic acid and maleic anhydride (sodium salt), in a proportion of about 2-4 20 Monobutyl ether of diethylene glycol in a proportion of about 5-15 Alkanol ester of phosphoric acid in a proportion of about 0.2-0.5 Sodium perborate monohydrate, bleach, in a proportion about 5-15 Benzoate-ethylidene acetate, bleach activator, in a proportion of about 2-6.0 30 Sequestering agent for the bleaching agent in a proportion of approximately 0.50-1.25 Anti-deposition agent in a proportion of approximately 0.5-1.5 15. A non-aqueous liquid detergent composition for heavy laundry according to claim 12, characterized in that it comprises; % by weight Non-ionic surfactant in a proportion of about 30-40 Non-ionic acid-terminated surfactant, viscosity improving agent, in a proportion of about 1-10 16. A method for cleaning soiled fabrics, characterized in that it comprises the contact of soiled fabrics with the detergent composition of claim 1. 17. The method of cleaning soiled fabrics of claim 16, characterized in that it comprises the contact of the soiled fabrics with the detergent composition for laundry of claim 12. 18. The method of claim 16 for cleaning soiled fabrics, characterized in that it comprises contacting the soiled fabrics with the laundry detergent composition of claim 14, 19. The method of claim 16 for cleaning soiled fabrics, characterized in that it comprises contacting the soiled fabrics with the detergent composition for washing powder of claim 15.